Reduction product of aryl dinitroso compounds



BEST AVAILABLE COPY Patented Dec. 14, 1943 mean BEST AVAlLABLE COPYElbert C. Ladd, Passaic, and William P. ter Horst, Packanack Lake, N.J., assignors to United States Rubber Company, New York, N. Y., acorporation of New Jersey No Drawing. Application August 29, 1941,Serial No. 408,756

17 Claims.

This invention relates to methods of reducing aryl dinitroso compoundsand to the reduced compounds.

This case is a continuaticn in-part of our application Serial No.327,630, filed April 3, 1940.

The invention broadly comprises an improved method of reducing aryldinitroso compounds, and particularly those of the class Consisting ofquinone dioxime peroxides, and aryl oxdiazole oxides such as arylfurazan oxides and aryl isooxdiazole oxides-by means of an alkalinesulfide such as the alkali-metal sulfides and the alkali earth metalsulfides. By alkali-metal herein is meant alkali-metals such as sodiumand potassium, etc., as Well as the hypothetical alkalimetal, ammonium.Examples of this class of reducing agent are sodium sulfide, sodiumhydrosulfide, ammonium sulfide, ammonium polysulfide, calciumhydrosulfide, etc. It has been found that when reducing agents of thistype react upon aryl dinitroso bodies, reaction products or reactionmixtures are formedwhich are useful as such. From such mixtures thedesired components may be separated by proper treatment, for example,quinone dioximes such as benzo-quinone dioximes, and aryl furazanes suchas benzofurazan.

' By the present method, elevated temperatures are not required sincethe reduction takes place rapidly at room temperature. solvents are notrequired. The reducing agents are relatively inexpensive and the yieldsof desired products are good and the formation of by-products isminimized.

' The reducing agent may be added to an aqueous suspension of thedinitroso compound in water or the reducing agent may be formed in situby passing hydrogen sulfide into an alkaline or ammoniacal suspension orsolution of the dinitrosocompound.

After the reduction the reaction mixture may be worked up by one ofseveral methods depending upon the type of product desired. This isillustrated by the following examples:

Example 1 136 grams (1 mol) of ortho-benzoquinone dioxime peroxide(probably are suspended in 700 cc, of water and 56 grams (1 mol.) ofNaSI-I or 80 grams of sodium sulfhydrate (70% NaSH) are gradually added,with Also expensive good stirring. During the addition the tempera-jture is maintained in the neighborhood of 25-35 C. by suitably cooling.After the addition is complete, stirring may be continued for a time toinsure completeness of the reaction. The reaction mixture is thenneutralized with or made slightly acid with a suitable acid, such assulfuric, and the precipitate which forms is filtered off, washed withwater and dried.

The product is a yellow solid which has a melting range of approximately125-135 C. A typical analysis is sulfur, 17.6%; nitrogen, 16.3%. Theproduct is partially soluble in bases, e. g., dilute ammonia water,giving a red solution. This solution when filtered and acidified yieldsa yellow precipitate which is practically free of sulfur, melts at140-145" C. and analyzes approximately 20.2% nitrogen. This product is1,2-benzoquinone dioxime =NOH That portion which is insoluble in thealkali burns with the blue flame characteristic of sulfur, and gives offS02 fumes when burned. Its melting rang is approximately 112120 C. Thisalkali insoluble portion accordingly is believed to be largely freesulfur, together with small amounts of other unidentified products.

The reaction product is suitable for use in fungicidal and insecticidalpreparations.

Example 2 In this example the procedure of Example 1 is followed up tothe point where the sodium sulfhydrate addition has been completed andthe mixture stirred for an adequate time. The reaction mixture is thenfiltered, the residue washed with water and the water washings added tothe main filtrate. The filtrate is then neutralized or mad just acidwith a suitable acid such as sulfuric. The yellow precipitate Whichforms is filtered off, washed with water and suitably dried. The productso obtained has a melting point of about 140-145" 0., is completelysoluble in dilute ammonia water to give a deep red solution. It analyzes20.2% nitrogen, and is practically free of sulfur, and consistsessentially of pure 1,2- benzoquinone dioxime.

Example 3 In this example the procedure of Example 1 is followed up tothe point where the addition of the sodium sulfhydrate has beencompleted,

BEST AVAlLABLE COPY and the mixture adequately stirred. The dioxime inthe reaction mixture is then converted into Example 4 467 parts byweight of 4-chloro-1,2- benzoquinone dioxime peroxide i-chlor-1,2-dinitrosobenzene) (probably are suspended in 2 litersof water, and220 parts of sodium sulfhydrate (70% NaSH) are added gradually with goodstirring. To insure maximum yield it is desirable to prevent thetemperature from rising materially above room temperature by suitablecooling during the addition, and preferably the reaction temperature issomewhat lower than room temperature (for example l-l5 C.). After theaddition has been completed, the reaction mixture may be stirred for atime to insure completeness of the reaction. The reaction mixture isneutralized or made just acid with a suitable acid such as sulfuric,whereupon a yellowish brown precipitate forms. The precipitate isfiltered off, washed with water and dried. The product has the followingcharacteristics: Melting range of about 95105 C. Typical analysis: 16.3%chlorine, 17.5% sulfur. The product is partially'soluble in diluteammonia water, the solution being deep red in color. Neutralization ofthe filtered solution precipitates a yellowish brown solid which ispractically free from sulfur, and which has a melting point of 110-115C. This portion of the product consists essentially of-chloro-1.,2-benzoquinone dioxide The ammonia insoluble portion appearsto be largely sulfur, since it burned with a blue flame and gave off S02when burned.

The reaction product may be used in insecticidal and fugicidalpreparations.

Example 5 The procedure of Example 4 is followed up to the point wherethe sodium sulfhydrate has been added and the mixture sufficientlystirred. The reaction mixture is then filtered, the residue washed withwater and the combined filtrates neutralized or just made acid with asuitable acid such as sulfuric acid, and the yellowish brown precipitatewhich is formed is filtered off, washed with water and dried. Theproduct has a melting point of 110-115 C. The nitrogen found is 15.9%.The product is essentially free of sulfur,

and consists of l-chloro-1,2-bcnzoquinone dioxime.

Example 6 The procedure of Example 4 is followed up to the place wherethe sodium sulfhydrate has been added, and the reaction mixtureadequately stirred. The dioxime in the reaction mixture is thenconverted into the corresponding furazan by the action of heat.Conveniently this may be done by steam distilling the mixture until awhite solid no longer comes over in the distillate. The solid is thenfiltered, washed With water and dried. The product has a melting pointof 38 1? C. and is soluble in many organic solvents including alcohol,acetone, benzene, kerosene, etc. The product is e-chloro-benzofurazan Inother modifications of the invention for the preparation of an aryldioxime, the dinitroso compound (1 mol) may be suspended in watercontaining the calculated amount of a basic materialsuch as ammonia orsodium hydroxide and the calculated amount (1 mol) of hydrogen sulfidepassed into the suspension with stirring and suitable cooling. Thepro-duct is worked up as described above. Also, in place of water orpartially in place of water a solvent such as ordinary alcohol may beused for the reaction medium.

The process is of general application for the preparation of that classof compounds described above as well as their analogs or homologs. Forexample, the process may be applied to the preparation of naphthoquinonedioximes and naphthofurazans from dinitroso-naphthalenes, to thepreparation of p-benzoquinone dioxime from pdinitrosobenzene,4-bromo-1,2-benzoquinone dioxime and 4-bromobenzofurazan from 4-bromo-1,2-benzoquinone dioxime peroxide, 4-methyl-1,2- benzoquinone dioximeand 4-methylbenzofurazan from 4-methy1 benziso-oxdiazole oxide, and thelike.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. A method which comprises reacting one mol weight of an aromaticdinitroso compound with approximately one mol-equivalent weight of analkaline sulfide whereby a mixture comprising a quinone dioxime and freesulphur is formed.

2. A method which comprises reacting one mol weight of a quinone dioximeperoxide with approximately one mol-equivalent weight of an alkalinesulfide, whereby a mixture comprising a quinone dioxime and free sulfuris formed.

3. A method which comprises reacting one mol weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkaline sulfide, whereby a mixture comprising an ortho quinone dioximeand free sulfur is formed.

4. A method which comprises reacting one mol weight of a haloquinonedioxime peroxide with approximately one mol-equivalent weight of analkali metal hydrosulfide, whereby a mixture comprising a haloquinonedioxime and free sulfur is formed.

5. Amethod which comprises reacting one mol weight of a4-hal-o-L2-benzoquinone dioxime peroxide with approximately onemol-equivalent weight of sodium hydrosulfide, whereby a mixturecomprising a 4-ha1o-1,2-benzoquinone dioxime and free sulfur is formed.

BEST AVAILABLE COPY 6. A method which comprises reducing one mol weightof a quinone dioxime peroxide with approximately one mol-equivalentweight of an alkaline sulfide, to a quinone dioxime.

7. A method which comprises reducing one mol weight of a quinone dioximeperoxide with approximately one mol-equivalent weight of an alkalinesulfide, thereafter neutralizing the mixture, and recovering a quinonedioxime.

8. A method which comprises reducing a halo- 1,2-benzoquinone dioximeperoxide with an alkali metal sulfide, thereafter neutralizing the mixture, and recovering a haloquinone dioxime.

9. A method which comprises reducing one mol weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkaline sulfide, thereafter neutralizing the mixture, and recovering anortho quinone dioxime.

10. A method which comprises reacting one mol weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkali metal sulfide whereby a quinone dioxime is formed, and thereafterconverting the dioxime to an aryl furazan by heat.

11. A method which comprises reducing one mol weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkali metal sulfide, steam distilling th reaction mix, and recoveringan aryl furazan from the distillate.

12. A method which comprises reducing one mol weight of ahalo-ortho-quinone dioxime peroxide with approximately onemol-equivalent Weight of an alkali metal sulfide, steam distilling thereaction mix, and recovering a halo-aryl furazan from the distillate.

13. A method which comprises reducing one mol weight of a para quinonedioxime peroxide with approximately one mol-equivalent weight of analkaline sulfide, thereafter neutralizing the mixture, and recoveringpara quinone dioxime.

14. A method which comprises reducing one mol weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkaline sulfide, steam distilling the reaction mix, and recovering anaryl furazan from the distillate.

15. A method which comprises reducing one mol Weight 'of ahalo-ortho-quinone dioxime peroxide with approximately onemol-equivalent weight of an alkaline sulfide, steam distilling thereaction mix, and recovering a halo-aryl furazan from the distillate.

16. A method which comprises reducing one mol Weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkaline sulfide, whereby an ortho quinone dioxime is formed.

17. A method which comprises reacting one mol Weight of an ortho quinonedioxime peroxide with approximately one mol-equivalent weight of analkalin sulfide whereby an ortho quinone dioxime is formed, andthereafter converting the dioxime to an aryl furazan by heat.

ELBERT C. LADD. WILLIAM P. TER HORST.

